CN102351693A - Preparation method for methoxyethyl methacrylate - Google Patents
Preparation method for methoxyethyl methacrylate Download PDFInfo
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- CN102351693A CN102351693A CN2011102422023A CN201110242202A CN102351693A CN 102351693 A CN102351693 A CN 102351693A CN 2011102422023 A CN2011102422023 A CN 2011102422023A CN 201110242202 A CN201110242202 A CN 201110242202A CN 102351693 A CN102351693 A CN 102351693A
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- stopper
- methacrylic acid
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- catalyzer
- ethyl ester
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a preparation method for methoxyethyl methacrylate. The method comprises the following steps of: reacting methyl methacrylate and methoxy ethanol serving as raw materials by using a reactive rectification transesterification process in the presence of a catalyst and a polymerization inhibitor; performing azeotropic distillation to timely remove methanol produced by reaction; distilling an obtained reaction product containing methoxyethyl methacrylate under a reduced pressure condition; and removing excessive methyl methacrylate and then removing the catalyst and the polymerization inhibitor to obtain a methoxyethyl methacrylate product, wherein the catalyst is a composite catalyst, and the polymerization inhibitor is a composite polymerization inhibitor. The preparation method has the advantages of good catalysis effect, short reaction time, high reaction efficiency, good polymerization inhibition effect, high reaction kettle efficiency, high product quality and yield and the like.
Description
One, technical field
The invention belongs to technical field of chemical synthesis, be specifically related to a kind of preparation method of methacrylic acid methoxy base ethyl ester.
Two, background technology
Methacrylic acid methoxy base ethyl ester is a kind of important two-component acrylicester adhesive and thermosetting acrylic resin, and the monomer of solution polymerization or suspension polymerization and comonomer.Be mainly used in ocean coating, biomaterial and paper industry.The preparation method of prior art methacrylic acid methoxy base ethyl ester mainly contains esterification process and ester-interchange method.
TQ225.241 has introduced a kind of with deposition-immersion process for preparing solid super-strong acid SO
4 2-/ TiO
2Be catalyzer, the method for synthesize methyl acrylic acid methoxyl group ethyl ester.This method adopts the esterification process operational path, active decline obviously after catalyst recirculation is used 2 times.
It is catalyzer with the p-methyl benzenesulfonic acid that TQ433.436 has introduced a kind of, and Resorcinol is a stopper, adopts the esterification process operational path, the method for acrylic acid synthesizing methoxyl group ethyl ester.
CN101475475 discloses and has a kind ofly prepared the method for vinylformic acid alcoxyl base ethyl ester or methacrylic acid alkoxyalkyl methacrylate through the esterification process operational path, is to be raw material with acrylic or methacrylic acid and ethylene glycol monoalkyl ether, with SO
4 2-/ TiO
2Solid super-strong acid is that catalyzer, thiodiphenylamine or thiodiphenylamine-Resorcinol-copper powder is that stopper, toluene are band aqua, direct esterification acrylic acid synthesizing alkoxyalkyl methacrylate or methacrylic acid alkoxyalkyl methacrylate.
Designed Monomers&Poymers (Volume12, Number5,2009) has introduced the synthetic corresponding methyl acrylic ester monomer methods of a kind of employing borate ester catalyzer, has wherein mentioned synthesize methyl acrylic acid methoxyl group ethyl ester.
It is raw material with (methyl) vinylformic acid low-carbon-ester and polyvalent alcohol that CN1355161 discloses a kind of, under composite catalyst (a)+(b) and stopper effect, through transesterification reaction preparation two (methyl) acrylic acid multielement alcohol ester.Wherein (a) refers to oxide compound, oxyhydroxide or the nitrate of calcium or barium; (b) refer to a kind of LiX compound, X can be nitric acid, sulfurous acid or 6 carboxylate salts that carbon atom is above.Stopper adopts piperidinol nitroxyl radical or piperidinol nitroxyl radical phosphorous acid ester.
US6008404 discloses the transesterification reaction that a kind of alkyl methacrylate and alcohols carry out, and catalyzer is an alkali metal alcoholates, and stopper is the bromine salt.
It is metal alkoxide that EP0574632 discloses a kind of transesterify catalyst system therefor.
US2002111511 discloses a kind of transesterify process of methylpropionate class, and catalyst system therefor is a) alkali metal cyanate or thiocyanate-, b) alkaline earth metal oxide, alkali metal hydroxide or halogenide, the mixture of the two.
Mostly the catalyzer of mentioning in above-mentioned document and the patent is that relevant methacrylic acid or methyl acrylic ester and alcohol carry out esterification or transesterification reaction and prepares methacrylic acid high alcohol ester class, and kind is more, and has nothing in common with each other, and solid super-strong acid SO is arranged
4 2-/ TiO
2, p-methyl benzenesulfonic acid, borate ester, calcium or oxide compound, oxyhydroxide or the nitrate of barium and carboxylate salt, alkali metal alcoholates, metal alkoxide, alkali metal cyanate or thiocyanate-and the alkaline earth metal oxide of nitric acid, sulfurous acid or 6 above lithiums of carbon atom; The two mixture etc. of alkali metal hydroxide or halogenide; But specific to preparation methacrylic acid methoxy base ethyl ester; The esterifications that adopt in the report more; This method not only on technology complicated operation, be prone to pollute; Also all there is different problems in the catalyzer of its use, like solid super-strong acid SO
4 2-/ TiO
2, an acidic catalyst such as toluene sulfonic acide, very strong corrodibility is all arranged as the one of which, equipment, apparatus and operational condition etc. are required all relatively harsher, and long reaction time, many, the serious three wastes of side reaction; Borate ester activity of such catalysts and selectivity are relatively low, and are prone in reaction process, take place disproportionation reaction.
In addition, because methacrylic acid high alcohol ester class contains unsaturated link(age), and has easy natural polymeric character after the light and heat of the being subjected to effect.Therefore, need add a certain amount of stopper in process of production.Usually the stopper of transesterification reaction use mainly contains Resorcinol, Hydroquinone monomethylether, thiodiphenylamine, piperidinol nitroxyl radical or piperidinol nitroxyl radical phosphorous acid ester, mantoquita etc.But these stoppers specifically are applied to shortcoming separately when preparing methacrylic acid methoxy base ethyl ester, the transesterification reaction of MMA and methyl cellosolve is arranged all.Like Resorcinol, large usage quantity, cost are higher, and just can show polymerization inhibition effect must in monomer, be dissolved with oxygen the time, can be entrained in the product during distillation, and quality product is impacted; Hydroquinone monomethylether only just has polymerization inhibition effect preferably to having the strong free radical of electronics of giving, and under hot conditions, can lose inhibition; Thiodiphenylamine causes the change of product colour because easy oxidation discoloration is easy oxidized in therefore producing; Piperidinol nitroxyl radical or piperidinol nitroxyl radical phosphorous acid ester, polymerization inhibition effect is better, but the price valency is high, and use separately sometimes, byproduct of reaction can increase; The copper salt kind stopper is difficult for dissolving, is prone to crystallization, through regular meeting's blocking pipe, and equipment had certain corrodibility.
Three, summary of the invention
The preparation method who the purpose of this invention is to provide a kind of methacrylic acid methoxy base ethyl ester, catalyzer that this method adopted and stopper can overcome existing not enough effectively.
For realizing above-mentioned purpose; The technical scheme that the present invention adopts is: this method is to be raw material with methyl methacrylate and methyl cellosolve; Under the condition of catalyzer and stopper existence; Adopt the reactive distillation ester exchange process to react; The methyl alcohol that reaction is generated in time removes through component distillation; And the reaction product that contains methacrylic acid methoxy base ethyl ester that will obtain is distilled under reduced pressure; After removing excessive methyl methacrylate; Remove catalyzer and stopper again, obtain methacrylic acid methoxy base ethyl ester product; Described catalyzer is a composite catalyst; Described stopper is a composite polymerzation inhibitor.
Above-mentioned composite catalyst is the mixture of category-A catalyzer and category-B catalyzer, and the mass ratio of category-A catalyzer and category-B catalyzer is 10:-1:10; The category-A catalyzer comprises in Zassol, potassium cyanate, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, Sodium Thiocyanate 99, the potassium sulfocyanate a kind of; The category-B catalyzer comprises a kind of in oxide compound or the oxyhydroxide of calcium, magnesium, lithium, barium.
Above-mentioned composite polymerzation inhibitor is the mixture of category-A stopper and category-B stopper, and the mass ratio of category-A stopper and category-B stopper is 10:-1:10; The category-A stopper comprises copper dibutyldithiocarbamate, 2,2,6,6-tetramethyl--4-hydroxy piperidine-1-oxygen nitroxyl free radical, tetramethyl piperidine nitrogen oxygen free radical tris phosphite, N, N
,A kind of in-(phenylbenzene)-p-phenylenediamine; The category-B stopper comprises 2,6-dinitro-p-cresol (DNPC), 2-sec-butyl-4, a kind of in 6-dinitrophenol(DNP) (DNBP), tert.-butyl phenol, the Resorcinol.
The add-on of above-mentioned composite catalyst is the 0.1%-5.0% of raw material total mass.
The add-on of above-mentioned composite polymerzation inhibitor is the 0.05%-0.5% of raw material total mass.
The consumption mol ratio of above-mentioned methyl methacrylate and methyl cellosolve is 1.5-6.5:1.
The concrete steps of the inventive method are: after 1. getting methyl methacrylate and methyl cellosolve in proportion and adding reaction kettle together; Add composite catalyst and composite polymerzation inhibitor more in proportion; Open and stir; Heat temperature raising is during to 80-130 ℃; Cat head begins discharging; Tower top temperature rises; After treating that tower top temperature is stabilized in 62-64 ℃; Open the trim the top of column system, the control reflux ratio is 6:1-6:2, and makes tower top temperature be stabilized in 63-70 ℃; Treat that the still temperature rise is between 115-125 ℃; And when tower top temperature has obvious rising, stop heating, cooling; 2. reaction solution is moved on to the separating still underpressure distillation, at first remove excessive methyl methacrylate, remove catalyzer, stopper and heavy component then, can obtain purity greater than 99.8% methacrylic acid methoxy base ethyl ester product from cat head.
The vacuum degree control that above-mentioned steps removes methyl methacrylate in 2. is at 10-15kPa, and tower top temperature is controlled at 40-50 ℃; The vacuum degree control that removes catalyzer, stopper and heavy component is at 0.01-2kPa, and tower top temperature is controlled at 70-110 ℃.
After the 1. middle rectifying ester exchange process reaction of above-mentioned steps finishes; Contain methyl methacrylate and methanol mixture is separated; After the mixture of separating was put into and purified in the tripping device, the methyl methacrylate of recovery can be recycled in next reaction, has reduced reaction cost.
The present invention has following beneficial effect: 1, the composite catalyst of Cai Yonging had both had the characteristics that consumption is few, catalytic efficiency is high, the reaction times is short, had reaction conditions gentleness, easy, the non-corrosiveness of aftertreatment again, but advantages such as recuperation utilization; 2, the composite polymerzation inhibitor of Cai Yonging had both had the advantage that consumption is few, high temperature resistant, polymerization inhibition effect is good, and having does not again influence advantages such as product color, aftertreatment are easy, non-corrosiveness.The employing of above-mentioned two kinds of efficient composite catalysts and stopper has not only reduced the content of polymers, has also effectively improved quality product and yield.3, owing to adopted the reactive distillation process technology; Form azeotrope through excessive methyl methacrylate and methyl alcohol; In time remove by-product carbinol; Promoted reaction to want that the direction that generates methacrylic acid methoxy base ethyl ester moves; Shortened the reaction times; Obviously reduce polymer content, improved the efficient of reaction kettle.
Four, embodiment
Embodiment 1: in reaction kettle, add 1184kg methyl methacrylate and 450kg methyl cellosolve; Add 44kg catalyzer (mixing), adding 4.4kg stopper (mixing) by tetramethyl piperidine nitrogen oxygen free radical tris phosphite and Resorcinol weight ratio by 2:1 by Zassol and the weight ratio of magnesium hydroxide by 2:1.
Open and stir, when heat temperature raising, reactor temperature rise to 90-100 ℃; Cat head begins discharging; Total reflux treats to open when tower top temperature is stabilized in 62-64 ℃ trim the top of column than system, and reflux ratio is 6:1-6:2; Make tower top temperature be stabilized in 63-70 ℃ through regulating reflux ratio; Treat the still temperature rise between 115-125 ℃, and tower top temperature when being arranged, obvious rising stops heating; Cooling, sampling analysis.
Product amounts to 1288kg in the still, forms (through gas chromatography determination):
Methyl alcohol 0.11%
Methyl cellosolve 1.22%
Methyl methacrylate 48.24%
Methacrylic acid methoxy base ethyl ester 49.72%
Reaction solution is moved on to separating still; The beginning decompression separation; In 1015kPa, tower top temperature is under the 40-50 ℃ of condition; Remove excessive methyl methacrylate; Be under the 70-110 ℃ of condition in 1-2000Pa, tower top temperature then; Remove catalyzer, stopper and heavy component, obtain purity greater than 99.8% methacrylic acid methoxy base ethyl ester product at the product receiving tank.
Embodiment 2: in reaction kettle, add 1316kg methyl methacrylate and 400kg methyl cellosolve; Add 86kg catalyzer (mixing), adding 8.6kg stopper (mixing) by copper dibutyldithiocarbamate and Resorcinol weight ratio by 2:1 by Zassol and the weight ratio of barium oxide by 5:1.
Open and stir, when heat temperature raising, reactor temperature rise to 90-100 ℃; Cat head begins discharging; Total reflux treats to open when tower top temperature is stabilized in 62-64 ℃ trim the top of column than system, and reflux ratio is 6:1-6:2; Make tower top temperature be stabilized in 63-70 ℃ through regulating reflux ratio; Treat the still temperature rise between 115-125 ℃, and tower top temperature when being arranged, obvious rising stops heating; Cooling, sampling analysis.
Product amounts to 1348kg in the still, forms (through gas chromatography determination):
Methyl alcohol 0.10%
Methyl cellosolve 1.04%
Methyl methacrylate 48.11%
Methacrylic acid methoxy base ethyl ester 49.96%
Reaction solution is moved on to separating still; The beginning decompression separation; In 10-15kPa, tower top temperature is under the 40-50 ℃ of condition; Remove excessive methyl methacrylate; Be under the 70-110 ℃ of condition in 1-2000Pa, tower top temperature then; Remove catalyzer, stopper and heavy component, obtain purity greater than 99.8% methacrylic acid methoxy base ethyl ester product at the product receiving tank.
Claims (9)
1. the preparation method of a methacrylic acid methoxy base ethyl ester; Be to be raw material with methyl methacrylate and methyl cellosolve; Under the condition of catalyzer and stopper existence; Adopt the reactive distillation ester exchange process to react; The methyl alcohol that reaction is generated in time removes through component distillation; And the reaction product that contains methacrylic acid methoxy base ethyl ester that will obtain is distilled under reduced pressure; After removing excessive methyl methacrylate; Remove catalyzer and stopper again, obtain methacrylic acid methoxy base ethyl ester product; Described catalyzer is a composite catalyst; Described stopper is a composite polymerzation inhibitor.
2. the preparation method of a kind of methacrylic acid methoxy base ethyl ester according to claim 1 is characterized in that: described composite catalyst is the mixture of category-A catalyzer and category-B catalyzer, and the mass ratio of category-A catalyzer and category-B catalyzer is 10:-1:10; The category-A catalyzer comprises in Zassol, potassium cyanate, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, Sodium Thiocyanate 99, the potassium sulfocyanate a kind of; The category-B catalyzer comprises a kind of in oxide compound or the oxyhydroxide of calcium, magnesium, lithium, barium.
3. the preparation method of a kind of methacrylic acid methyl cellosolve ester according to claim 1 is characterized in that: described composite polymerzation inhibitor is the mixture of category-A stopper and category-B stopper, and the mass ratio of category-A stopper and category-B stopper is 10:-1:10; The category-A stopper comprises copper dibutyldithiocarbamate, 2,2,6,6-tetramethyl--4-hydroxy piperidine-1-oxygen nitroxyl free radical, tetramethyl piperidine nitrogen oxygen free radical tris phosphite, N, N
,A kind of in-(phenylbenzene)-p-phenylenediamine; The category-B stopper comprises 2,6-dinitro-p-cresol (DNPC), 2-sec-butyl-4, a kind of in 6-dinitrophenol(DNP) (DNBP), tert.-butyl phenol, the Resorcinol.
4. the preparation method of a kind of methacrylic acid methoxy base ethyl ester according to claim 1 is characterized in that: the add-on of described composite catalyst is the 0.1%-5.0% of raw material total mass.
5. the preparation method of a kind of methacrylic acid methoxy base ethyl ester according to claim 1 is characterized in that: the add-on of described composite polymerzation inhibitor is the 0.05%-0.5% of raw material total mass.
6. the preparation method of a kind of methacrylic acid methoxy base ethyl ester according to claim 1 is characterized in that: the consumption mol ratio of described methyl methacrylate and methyl cellosolve is 1.5-6.5:1.
7. the preparation method of a kind of methacrylic acid methoxy base ethyl ester according to claim 1; It is characterized in that: the concrete steps of described the inventive method are: after 1. getting methyl methacrylate and methyl cellosolve in proportion and adding reaction kettle together; Add composite catalyst and composite polymerzation inhibitor more in proportion; Open and stir; Heat temperature raising is during to 80-130 ℃; Cat head begins discharging; Tower top temperature rises, treat that tower top temperature is stabilized in 62-64 ℃ after, open the trim the top of column system; The control reflux ratio is 6:1-6:2; And make tower top temperature be stabilized in 63-70 ℃, treat the still temperature rise between 115-125 ℃, and tower top temperature is when having obvious rising; Stop heating, cooling; 2. reaction solution is moved on to the separating still underpressure distillation, at first remove excessive methyl methacrylate, remove catalyzer, stopper and heavy component then, can obtain methacrylic acid methoxy base ethyl ester product from cat head.
8. the preparation method of a kind of methacrylic acid methoxy base ethyl ester according to claim 7 is characterized in that: the vacuum degree control that step removes methyl methacrylate in 2. is at 10-15kPa, and tower top temperature is controlled at 40-50 ℃; The vacuum degree control that removes catalyzer, stopper and heavy component is at 0.01-2kPa, and tower top temperature is controlled at 70-110 ℃.
9. the preparation method of a kind of methacrylic acid methoxy base ethyl ester according to claim 7; It is characterized in that: after the 1. middle rectifying ester exchange process reaction of step finishes; Contain methyl methacrylate and methanol mixture is separated; After the mixture of separating was put into and purified in the tripping device, the methyl methacrylate of recovery can be recycled in next reaction.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102850217A (en) * | 2012-09-24 | 2013-01-02 | 上海和创化学有限公司 | Method for preparing methoxyethyl acrylate and methoxyethyl methacrylate |
CN103755564A (en) * | 2013-12-19 | 2014-04-30 | 抚顺安信化学有限公司 | Preparation method for ethoxyethyl methacrylate |
CN103755565A (en) * | 2013-12-19 | 2014-04-30 | 抚顺安信化学有限公司 | Preparation method of neopentyl glycol dimethacrylate |
CN105330537A (en) * | 2015-11-30 | 2016-02-17 | 抚顺东联安信化学有限公司 | Preparation method of methoxyethyl acrylate |
CN108586271A (en) * | 2018-06-05 | 2018-09-28 | 李守莉 | A kind of preparation method of diethylaminoethyl methacrylate |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4117238A (en) * | 1975-06-05 | 1978-09-26 | Deutsche Gold-Und Silber-Scheideanstalt Vormals Roessler | Process for the trans-esterification of acrylic and methacrylic esters |
US4464539A (en) * | 1980-10-16 | 1984-08-07 | Mitsui Toatsu Chemicals, Inc. | Process for producing α,β-unsaturated carboxylic acids or esters thereof |
EP0574632A1 (en) * | 1992-06-17 | 1993-12-22 | Rohm And Haas Company | Preparation of carboxylic acid esters |
CN1127745A (en) * | 1995-01-26 | 1996-07-31 | 中国石化齐鲁石油化工公司 | Method for preparing alkyl acrylate (or methylacrylate) |
US6008404A (en) * | 1997-08-11 | 1999-12-28 | Ciba Specialty Chemicals Corporation | Acrylate monomer preparation using alkali metal alkoxides as ester interchange catalysts and bromide salt polymerization inhibitors |
CN1355161A (en) * | 2000-11-24 | 2002-06-26 | 中国石化集团齐鲁石油化工公司 | Process for preparing polyol di(methy) acrylate |
US20020111511A1 (en) * | 2001-02-12 | 2002-08-15 | Roehm Gmbh & Co. Kg | Process for synthesis of (meth) acrylic acid esters by transesterification in the presence of mixed catalysts containing alkali metal cyanate or thiocyanate |
CN101475475A (en) * | 2009-01-21 | 2009-07-08 | 南京林业大学 | Method for synthesizing acrylic alkoxy ethyl ester or methacrylate alkoxy ethyl ester |
CN101514158A (en) * | 2009-04-03 | 2009-08-26 | 上海和创化学有限公司 | Preparation method of ethylene glycol dimethacrylate |
CN102030641A (en) * | 2010-12-08 | 2011-04-27 | 里光 | Method for preparing 1,4-butanediol dimethacrylate |
-
2011
- 2011-08-23 CN CN2011102422023A patent/CN102351693A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4117238A (en) * | 1975-06-05 | 1978-09-26 | Deutsche Gold-Und Silber-Scheideanstalt Vormals Roessler | Process for the trans-esterification of acrylic and methacrylic esters |
US4464539A (en) * | 1980-10-16 | 1984-08-07 | Mitsui Toatsu Chemicals, Inc. | Process for producing α,β-unsaturated carboxylic acids or esters thereof |
EP0574632A1 (en) * | 1992-06-17 | 1993-12-22 | Rohm And Haas Company | Preparation of carboxylic acid esters |
CN1127745A (en) * | 1995-01-26 | 1996-07-31 | 中国石化齐鲁石油化工公司 | Method for preparing alkyl acrylate (or methylacrylate) |
US6008404A (en) * | 1997-08-11 | 1999-12-28 | Ciba Specialty Chemicals Corporation | Acrylate monomer preparation using alkali metal alkoxides as ester interchange catalysts and bromide salt polymerization inhibitors |
CN1355161A (en) * | 2000-11-24 | 2002-06-26 | 中国石化集团齐鲁石油化工公司 | Process for preparing polyol di(methy) acrylate |
US20020111511A1 (en) * | 2001-02-12 | 2002-08-15 | Roehm Gmbh & Co. Kg | Process for synthesis of (meth) acrylic acid esters by transesterification in the presence of mixed catalysts containing alkali metal cyanate or thiocyanate |
CN101475475A (en) * | 2009-01-21 | 2009-07-08 | 南京林业大学 | Method for synthesizing acrylic alkoxy ethyl ester or methacrylate alkoxy ethyl ester |
CN101514158A (en) * | 2009-04-03 | 2009-08-26 | 上海和创化学有限公司 | Preparation method of ethylene glycol dimethacrylate |
CN102030641A (en) * | 2010-12-08 | 2011-04-27 | 里光 | Method for preparing 1,4-butanediol dimethacrylate |
Non-Patent Citations (2)
Title |
---|
《化学反应工程与工艺》 20100228 雷海琴 等 "SO_4_2_TiO_2催化合成甲基丙烯酸甲氧基乙酯" 第19-23页 1-9 第26卷, 第1期 * |
雷海琴 等: ""SO_4_2_TiO_2催化合成甲基丙烯酸甲氧基乙酯"", 《化学反应工程与工艺》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102850217A (en) * | 2012-09-24 | 2013-01-02 | 上海和创化学有限公司 | Method for preparing methoxyethyl acrylate and methoxyethyl methacrylate |
CN102850217B (en) * | 2012-09-24 | 2015-10-28 | 上海和创化学股份有限公司 | The preparation method of methoxyethyl acrylate and methoxyethyl methacrylate |
CN103755564A (en) * | 2013-12-19 | 2014-04-30 | 抚顺安信化学有限公司 | Preparation method for ethoxyethyl methacrylate |
CN103755565A (en) * | 2013-12-19 | 2014-04-30 | 抚顺安信化学有限公司 | Preparation method of neopentyl glycol dimethacrylate |
CN103755565B (en) * | 2013-12-19 | 2017-03-29 | 抚顺东联安信化学有限公司 | The preparation method of neopentyl glycol dimethacrylate |
CN105330537A (en) * | 2015-11-30 | 2016-02-17 | 抚顺东联安信化学有限公司 | Preparation method of methoxyethyl acrylate |
CN108586271A (en) * | 2018-06-05 | 2018-09-28 | 李守莉 | A kind of preparation method of diethylaminoethyl methacrylate |
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Application publication date: 20120215 |